Herbicidal 1-pyridyltetrazolinones

ABSTRACT

Herbicidal tetrazolinone derivatives of the formula: ##STR1## in which R 1  is alkyl, haloalkyl, cycloalkyl, alkenyl, haloalkenyl, alkynyl or phenyl, and 
     R 2  is alkyl, haloalkyl, cycloalkyl, alkenyl, haloalkenyl, alkynyl or phenyl, or 
     R 1  and R 2  together with the nitrogen atom to which they are bonded form an optionally benzofused heterocyclic ring, which is optionally substituted by C 1-4  alkyl, 
     n is 0, 1, 2 or 3, and 
     R 3  each independently is nitro, halogen, alkyl, haloalkyl, alkylthio or phenoxy.

The present invention relates to tetrazolinone derivatives, to processes for their preparation and to their use as herbicides, as well as to intermediates therefor.

It has already been known that tetrazolinone derivatives are useful as herbicides (see U.S. Pat. Nos. 4,618,365; 4,826,529; 4,830,661; 4,956,469; 5,003,075; 5,019,152; 5,342,954; 5,344,814; 5,347,009; 5,347,010 and 5,362,704).

There have been found novel tetrazolinone derivatives of the formula (I) ##STR2## wherein

R¹ is alkyl, haloalkyl, cycloalkyl, alkenyl, haloalkenyl, alkynyl or phenyl which may be substituted, and

R² is alkyl, haloalkyl, cycloalkyl, alkenyl, haloalkenyl, alkynyl or phenyl which may be substituted, or

R¹ and R² may form, together with the nitrogen atom to which R¹ and R² are bonded, a 5- or 6-membered heterocyclic ring, said heterocyclic ring may be benzofused and may be substituted by one or more C₁₋₄ alkyl radicals,

R³ is nitro, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio or phenoxy, and

n is 0, 1, 2 or 3, and when n is 2 or 3, then R³ may be same or different.

The novel tetrazolinone derivatives of the formula (I) are obtained when

(a) compounds of the following formula (II) ##STR3## wherein R³ and n have the above mentioned meanings, are reacted with compounds of the following formula (III) ##STR4## wherein R¹ and R² have the above mentioned meanings, and hal represents a releasable group such as chlorine or bromine, in the presence of acid-binder, in the presence of inert solvents.

The novel tetrazolinone derivatives of the formula (I) exhibit powerful herbicidal properties.

Surprisingly, the tetrazolinone derivatives of the formula (I) according to the present invention exhibit a substantially higher herbicidal activity than those known from the prior art, for instance, the aforementioned U.S. Pat. Nos. 4,618,365; 4,826,529; 4,830,661; 4,956,469; 5,003,075; 5,019,152; 5,342,954; 5,344,814; 5,347,009; 5,347,010 and 5,362,704.

In the compounds of the formula (I) according to the invention, and the respective general formulae representing their intermediates employed for the production of the compounds formula (1), each of the halogen as well as the halogen parts of the haloalkyl, haloalkenyl and haloalkoxy represent fluorine, chlorine, bromine or iodine, preferably chlorine or fluorine.

Alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-(iso-, sec-, tert-)butyl, n-(iso-, sec-, tert-, neo-)pentyl or n-(iso-, see-, tert-, neo-)hexyl.

Haloalkyl is the above mentioned alkyl groups substituted with the same or different halogen atoms, such as for example, trifluoromethyl, 2-chloroethyl and 2,2,2-trifluoroethyl.

Cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

Alkenyl is, for example, vinyl, allyl, isopropenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-(or 3-)butenyl or 2-(3- or 4-)pentenyl.

Haloalkenyl is the above mentioned alkenyl groups substituted with the same or different halogen atoms, such as for example, 2-chloro-2-propenyl.

The alkynyl represents, for example, propargyl.

The 5- or 6-membered heterocyclic ring contains, as a hetero-atom, at least one nitrogen and may contain further hetero-atoms selected from the group consisting of nitrogen, oxygen and sulfur. Said heterocyclic group may be benzofused, and for example, pyrrolidinyl, 2,5-dimethylpyrrolidinyl, pyrrolinyl, 2,5-dimethyl-3-pyrrolinyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl, piperidyl, 2-methylpiperidyl, 2,6-dimethylpiperidyl, piperazinyl, indolinyl, morpholinyl, 1,2,3,4-tetrahydroquinolyl or 2-methyl-1,2,3,4-tetrahydroquinolyl can be exemplified.

Phenyl and phenoxy may optionally be substituted. The substitutent(s) are selected from the group consisting of halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy and alkylthio.

Alkoxy is for example, methoxy, ethoxy, propoxy, isopropoxy, n-(iso-, sec-, tert-)butoxy, n-(iso-, sec-, tert-, neo-)pentoxy or n-(iso-, sec-, tert-, neo-)hextoxy.

Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-(iso-, sec-, tert-)butylthio, n-(iso-, sec-, tert-, neo-)pentylthio or n-(iso-, sec-, ten-, neo-)hexylthio.

Haloalkoxy is the above mentioned alkoxy substituted with the same or different halogen atoms, for example, trifluoromethoxy.

Among the tetrazolinone derivatives according to the invention, of the formula (I), preferred compounds are those in which

R¹ is C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₃₋₈ cycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₃₋₆ alkynyl or phenyl, and

R² is C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₃₋₈ cycloalkyl, C²⁻⁶ alkenyl, C₂₋₆ haloalkenyl, C³⁻⁶ alkynyl or phenyl, or

R¹ and R² may form, together with the nitrogen atom to which R¹ and R² are bonded, a 5- or 6-membered heterocyclic ring, the hetero atoms of which are selected from the group consisting of nitrogen atom, oxygen and sulfur and said heterocyclic ring may be benzofused and may be substituted by one or more methyl radicals,

R³ is nitro, fluoro, chloro, bromo, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄ alkylthio or phenoxy, and

n is 0, 1, 2 or 3, and when n is 2 or 3, R³ may be same or different.

Particularly preferred tetrazolinone derivatives of the formula (I) are those in which

R¹ is C₁₋₄ alkyl, C₁₋₄ haloalkyl, cyclopropyl, cyclopentyl, cyclohexyl, C₂₋₄ alkenyl, C₂₋₄ haloalkenyl, C₃₋₄ alkynyl or phenyl, and

R² is C₁₋₄ alkyl, C₁₋₄ haloalkyl, cyclopropyl, cyclopentyl, cyclohexyl, C₂₋₄ alkenyl, C₂₋₄ haloalkenyl, C₃₋₄ alkynyl or phenyl, or

R¹ and R² may form, together with the nitrogen atom to which R¹ and R² are bonded, pyrrolidinyl, 2,5-dimethylpyrrolidinyl, pyrrolinyl, 2,5-dimethyl-3-pyrrolinyl, piperidyl, 2-methylpiperidyl, 2,6-dimethylpiperidyl, piperazinyl, morpholinyl, 1,2,3,4-tetrahydroquinolyl or 2-methyl- 1,2,3,4-tetrahydroquinolyl.

R³ is nitro, fluoro, chloro, bromo, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄ alkylthio or phenoxy, and

n is 0, 1 or 2, and when n is 2, R³ may be same or different.

Specifically, compounds according to the invention wherein R¹ and R² represent each an independent group are shown in the Table 1, and those wherein R¹ and R² together with the nitrogen to which they are bonded form a heterocyclic ring are shown in the Table 2. ##STR5##

                  TABLE 1                                                          ______________________________________                                         Q          R.sup.1       R.sup.2                                               ______________________________________                                         Q1         methyl        isopropyl                                             Q1         methyl        cyclopropyl                                           Q1         ethyl         ethyl                                                 Q1         ethyl         isopropyl                                             Q1         ethyl         cyclopropyl                                           Q1         ethyl         cyclohexyl                                            Q1         n-propyl      isopropyl                                             Q1         isopropyl     isopropyl                                             Q1         isopropyl     phenyl                                                Q2         methyl        ethyl                                                 Q2         methyl        isopropyl                                             Q2         methyl        cyclopropyl                                           Q2         ethyl         ethyl                                                 Q2         ethyl         isopropyl                                             Q2         ethyl         cyclopropyl                                           Q2         n-propyl      cyclopropyl                                           Q2         isopropyl     isopropyl                                             Q2         isopropyl     cyclohexyl                                            Q3         methyl        methyl                                                Q3         methyl        isopropyl                                             Q3         methyl        cyclopropyl                                           Q3         ethyl         ethyl                                                 Q3         ethyl         n-propyl                                              Q3         ethyl         isopropyl                                             Q3         ethyl         cyclohexyl                                            Q3         n-propyl      isopropyl                                             Q3         isopropyl     isopropyl                                             Q3         isopropyl     phenyl                                                Q4         methyl        n-propyl                                              Q4         methyl        isopropyl                                             Q4         methyl        cyclopropyl                                           Q4         methyl        cyclohexyl                                            Q4         methyl        1-methyl-2-propenyl                                   Q4         ethyl         ethyl                                                 Q4         ethyl         isopropyl                                             Q4         ethyl         cyclopropyl                                           Q4         ethyl         cyclohexyl                                            Q4         2-chloroethyl isopropyl                                             Q4         2-chloroethyl 2-chloroethyl                                         Q4         isopropyl     2,2,2-trifluoroethyl                                  Q4         n-propyl      isopropyl                                             Q4         n-propyl      cyclopropyl                                           Q4         n-propyl      cyclohexyl                                            Q4         isopropyl     isopropyl                                             Q4         isopropyl     phenyl                                                Q4         isopropyl     propargyl                                             Q4         allyl         allyl                                                 Q4         propargyl     propargyl                                             Q4         isopropyl     allyl                                                 Q5         methyl        methyl                                                Q5         methyl        ethyl                                                 Q5         methyl        n-propyl                                              Q5         methyl        isopropyl                                             Q5         methyl        cyclopropyl                                           Q5         methyl        1-methyl-2-propenyl                                   Q5         methyl        cyclopentyl                                           Q5         ethyl         ethyl                                                 Q5         ethyl         n-propyl                                              Q5         ethyl         isopropyl                                             Q5         ethyl         sec-butyl                                             Q5         ethyl         cyclopropyl                                           Q5         ethyl         cyclohexyl                                            Q5         ethyl         2,2,2-trifluoroethyl                                  Q5         n-propyl      2,2,2-trifluoroethyl                                  Q5         isopropyl     2,2,2-trifluoroethyl                                  Q5         2-chloroethyl ethyl                                                 Q5         2-chloroethyl n-propyl                                              Q5         2-chloroethyl isopropyl                                             Q5         2-chloroethyl 2-chloroethyl                                         Q5         n-propyl      isopropyl                                             Q5         n-propyl      cyclopropyl                                           Q5         n-propyl      cyclohexyl                                            Q5         isopropyl     isopropyl                                             Q5         isopropyl     phenyl                                                Q5         isopropyl     allyl                                                 Q5         isopropyl     2-chloro-2-propenyl                                   Q5         isopropyl     2-methyl-2-propenyl                                   Q5         isopropyl     propargyl                                             Q5         allyl         allyl                                                 Q5         propargyl     propargyl                                             Q6         methyl        methyl                                                Q6         methyl        isopropyl                                             Q6         methyl        cyclopropyl                                           Q6         methyl        cyclopentyl                                           Q6         methyl        1-methyl-2-propenyl                                   Q6         ethyl         ethyl                                                 Q6         ethyl         isopropyl                                             Q6         ethyl         cyclopropyl                                           Q6         ethyl         cyclohexyl                                            Q6         isopropyl     2,2,2-trifluoroethyl                                  Q6         2-chloroethyl isopropyl                                             Q6         2-chloroethyl 2-chloroethyl                                         Q6         n-propyl      isopropyl                                             Q6         n-propyl      cyclopropyl                                           Q6         n-propyl      cyclopentyl                                           Q6         isopropyl     isopropyl                                             Q6         isopropyl     cyclohexyl                                            Q6         isopropyl     phenyl                                                Q6         isopropyl     allyl                                                 Q6         isopropyl     propargyl                                             Q6         allyl         allyl                                                 Q6         propargyl     propargyl                                             Q7         methyl        isopropyl                                             Q7         methyl        cyclopropyl                                           Q7         ethyl         ethyl                                                 Q7         ethyl         isopropyl                                             Q7         ethyl         cyclopropyl                                           Q7         n-propyl      isopropyl                                             Q7         isopropyl     isopropyl                                             Q7         isopropyl     phenyl                                                Q8         methyl        methyl                                                Q8         methyl        isopropyl                                             Q8         methyl        cyclopropyl                                           Q8         methyl        cyclohexyl                                            Q8         methyl        1-methyl-2-propenyl                                   Q8         ethyl         ethyl                                                 Q8         ethyl         isopropyl                                             Q8         ethyl         cyclopropyl                                           Q8         ethyl         cyclopentyl                                           Q8         ethyl         2,2,2-trifluoroethyl                                  Q8         n-propyl      2,2,2-trifluoroethyl                                  Q8         iso-propyl    2,2,2-trifluoroethyl                                  Q8         2-chloroethyl ethyl                                                 Q8         2-chloroethyl n-propyl                                              Q8         2-chloroethyl isopropyl                                             Q8         2-chloroethyl 2-chloroethyl                                         Q8         n-propyl      isopropyl                                             Q8         n-propyl      cyclopropyl                                           Q8         n-propyl      cyclohexyl                                            Q8         isopropyl     isopropyl                                             Q8         isopropyl     phenyl                                                Q8         isopropyl     allyl                                                 Q8         isopropyl     2-chloro-2-propenyl                                   Q8         isopropyl     2-methyl-2-propenyl                                   Q8         isopropyl     propargyl                                             Q8         allyl         allyl                                                 Q8         propargyl     propargyl                                             Q9         methyl        ethyl                                                 Q9         methyl        isopropyl                                             Q9         methyl        cyclopropyl                                           Q9         methyl        s-butyl                                               Q9         methyl        1-methyl-2-propenyl                                   Q9         ethyl         ethyl                                                 Q9         ethyl         n-propyl                                              Q9         ethyl         isopropyl                                             Q9         ethyl         cyclopropyl                                           Q9         isopropyl     2,2,2-trifluoroethyl                                  Q9         2-chloroethyl isopropyl                                             Q9         2-chloroethyl 2-chloroethyl                                         Q9         n-propyl      isopropyl                                             Q9         n-propyl      cyclopropyl                                           Q9         n-propyl      s-butyl                                               Q9         isopropyl     isopropyl                                             Q9         isopropyl     cyclohexyl                                            Q9         isopropyl     phenyl                                                Q9         isopropyl     allyl                                                 Q9         isopropyl     propargyl                                             Q9         allyl         allyl                                                 Q9         propargyl     propargyl                                             Q10        methyl        n-propyl                                              Q10        methyl        isopropyl                                             Q10        methyl        cyclopropyl                                           Q10        methyl        s-butyl                                               Q10        methyl        1-methyl-2-propenyl                                   Q10        ethyl         ethyl                                                 Q10        ethyl         n-propyl                                              Q10        ethyl         isopropyl                                             Q10        ethyl         cyclopropyl                                           Q10        ethyl         phenyl                                                Q10        isopropyl     2,2,2-trifluoroethyl                                  Q10        2-chloroethyl isopropyl                                             Q10        2-chloroethyl 2-chloroethyl                                         Q10        n-propyl      isopropyl                                             Q10        n-propyl      cyclopropyl                                           Q10        n-propyl      s-butyl                                               Q10        isopropyl     cyclohexyl                                            Q10        isopropyl     phenyl                                                Q10        isopropyl     allyl                                                 Q10        isopropyl     propargyl                                             Q10        allyl         allyl                                                 Q10        propargyl     propargyl                                             Q11        methyl        isopropyl                                             Q11        ethyl         ethyl                                                 Q11        ethyl         isopropyl                                             Q11        ethyl         s-butyl                                               Q11        ethyl         phenyl                                                Q11        n-propyl      isopropyl                                             Q11        isopropyl     phenyl                                                Q12        methyl        n-propyl                                              Q12        methyl        isopropyl                                             Q12        methyl        cyclopropyl                                           Q12        methyl        1-methyl-2-propenyl                                   Q12        ethyl         ethyl                                                 Q12        ethyl         isopropyl                                             Q12        ethyl         cyclopropyl                                           Q12        ethyl         cyclohexyl                                            Q12        isopropyl     2,2,2-trifluoroethyl                                  Q12        2-chloroethyl isopropyl                                             Q12        2-chloroethyl 2-chloroethyl                                         Q12        n-propyl      isopropyl                                             Q12        n-propyl      cyclopropyl                                           Q12        n-propyl      cyclohexyl                                            Q12        isopropyl     isopropyl                                             Q12        isopropyl     phenyl                                                Q12        isopropyl     allyl                                                 Q12        isopropyl     propargyl                                             Q12        allyl         allyl                                                 Q12        propargyl     propargyl                                             Q13        methyl        isopropyl                                             Q13        methyl        cyclopropyl                                           Q13        methyl        cyclohexyl                                            Q13        methyl        1-methyl-2-propenyl                                   Q13        ethyl         ethyl                                                 Q13        ethyl         isopropyl                                             Q13        ethyl         cyclopropyl                                           Q13        ethyl         cyclohexyl                                            Q13        isopropyl     2,2,2-trifluoroethyl                                  Q13        2-chloroethyl isopropyl                                             Q13        2-chloroethyl 2-chloroethyl                                         Q13        n-propyl      isopropyl                                             Q13        n-propyl      cyclopropyl                                           Q13        isopropyl     isopropyl                                             Q13        isopropyl     phenyl                                                Q13        isopropyl     allyl                                                 Q13        isopropyl     propargyl                                             Q13        allyl         allyl                                                 Q13        propargyl     propargyl                                             Q14        methyl        methyl                                                Q14        methyl        ethyl                                                 Q14        methyl        n-propyl                                              Q14        methyl        isopropyl                                             Q14        methyl        cyclopropyl                                           Q14        methyl        cyclopentyl                                           Q14        methyl        1-methyl-2-propenyl                                   Q14        ethyl         ethyl                                                 Q14        ethyl         n-propyl                                              Q14        ethyl         sec-butyl                                             Q14        ethyl         isopropyl                                             Q14        ethyl         cyclopropyl                                           Q14        ethyl         cyclohexyl                                            Q14        ethyl         2,2,2-trifluoroethyl                                  Q14        n-propyl      2,2,2-trifluoroethyl                                  Q14        isopropyl     2,2,2-trifluoroethyl                                  Q14        2-chloroethyl ethyl                                                 Q14        2-chloroethyl n-propyl                                              Q14        2-chloroethyl isopropyl                                             Q14        2-chloroethyl 2-chloroethyl                                         Q14        n-propyl      isopropyl                                             Q14        n-propyl      cyclopropyl                                           Q14        isopropyl     isopropyl                                             Q14        isopropyl     2-chloro-2-propenyl                                   Q14        isopropyl     2-methyl-2-propenyl                                   Q14        isopropyl     propargyl                                             Q14        isopropyl     phenyl                                                Q14        isopropyl     allyl                                                 Q14        allyl         allyl                                                 Q14        propargyl     propargyl                                             Q15        methyl        isopropyl                                             Q15        methyl        cyclopropyl                                           Q15        methyl        1-methyl-2-propenyl                                   Q15        ethyl         ethyl                                                 Q15        ethyl         isopropyl                                             Q15        ethyl         cyclopropyl                                           Q15        ethyl         cyclohexyl                                            Q15        isopropyl     2,2,2-trifluoroethyl                                  Q15        2-chloroethyl isopropyl                                             Q15        2-chloroethyl 2-chloroethyl                                         Q15        n-propyl      isopropyl                                             Q15        n-propyl      cyclopropyl                                           Q15        isopropyl     isopropyl                                             Q15        isopropyl     phenyl                                                Q15        isopropyl     allyl                                                 Q15        isopropyl     propargyl                                             Q15        allyl         allyl                                                 Q15        propargyl     propargyl                                             Q16        methyl        isopropyl                                             Q16        methyl        cyclopropyl                                           Q16        methyl        1-methyl-2-propenyl                                   Q16        ethyl         ethyl                                                 Q16        ethyl         isopropyl                                             Q16        ethyl         cyclopropyl                                           Q16        ethyl         cyclohexyl                                            Q16        isopropyl     2,2,2-trifluoroethyl                                  Q16        2-chloroethyl isopropyl                                             Q16        2-chloroethyl 2-chloroethyl                                         Q16        n-propyl      isopropyl                                             Q16        n-propyl      cyclopropyl                                           Q16        isopropyl     isopropyl                                             Q16        isopropyl     phenyl                                                Q16        isopropyl     allyl                                                 Q16        isopropyl     propargyl                                             Q16        allyl         allyl                                                 Q16        propargyl     propargyl                                             Q17        methyl        isopropyl                                             Q17        methyl        cyclopropyl                                           Q17        n-propyl      isopropyl                                             Q17        methyl        1-methyl-2-propenyl                                   Q17        ethyl         ethyl                                                 Q17        ethyl         isopropyl                                             Q17        ethyl         cyclopropyl                                           Q17        isopropyl     2,2,2-trifluoroethyl                                  Q17        2-chloroethyl isopropyl                                             Q17        2-chloroethyl 2-chloroethyl                                         Q17        n-propyl      cyclopropyl                                           Q17        isopropyl     isopropyl                                             Q17        isopropyl     phenyl                                                Q17        isopropyl     allyl                                                 Q17        isopropyl     propargyl                                             Q17        allyl         allyl                                                 Q17        propargyl     propargyl                                             Q18        methyl        isopropyl                                             Q18        methyl        cyclopropyl                                           Q18        methyl        phenyl                                                Q18        methyl        1-methyl-2-propenyl                                   Q18        ethyl         ethyl                                                 Q18        ethyl         n-propyl                                              Q18        ethyl         isopropyl                                             Q18        ethyl         cyclopropyl                                           Q18        isopropyl     2,2,2-trifluoroethyl                                  Q18        2-chloroethyl isopropyl                                             Q18        2-chloroethyl 2-chloroethyl                                         Q18        n-propyl      isopropyl                                             Q18        isopropyl     isopropyl                                             Q18        isopropyl     phenyl                                                Q18        isopropyl     allyl                                                 Q18        isopropyl     propargyl                                             Q18        allyl         allyl                                                 Q18        propargyl     propargyl                                             Q19        methyl        methyl                                                Q19        methyl        ethyl                                                 Q19        methyl        isopropyl                                             Q19        methyl        cyclopropyl                                           Q19        methyl        1-methyl-2-propenyl                                   Q19        ethyl         ethyl                                                 Q19        ethyl         isopropyl                                             Q19        ethyl         cyclopropyl                                           Q19        ethyl         2,2,2-trifluoroethyl                                  Q19        n-propyl      2,2,2-trifluoroethyl                                  Q19        isopropyl     2,2,2-trifluoroethyl                                  Q19        2-chloroethyl ethyl                                                 Q19        2-chloroethyl n-propyl                                              Q19        2-chloroethyl isopropyl                                             Q19        2-chloroethyl 2-chloroethyl                                         Q19        n-propyl      isopropyl                                             Q19        isopropyl     isopropyl                                             Q19        isopropyl     phenyl                                                Q19        isopropyl     allyl                                                 Q19        isopropyl     2-chloro-propenyl                                     Q19        isopropyl     2-methyl-propenyl                                     Q19        isopropyl     propargyl                                             Q19        allyl         allyl                                                 Q19        propargyl     propargyl                                             Q20        methyl        isopropyl                                             Q20        methyl        1-methyl-2-propenyl                                   Q20        ethyl         ethyl                                                 Q20        ethyl         isopropyl                                             Q20        ethyl         cyclopropyl                                           Q20        2-chloroethyl isopropyl                                             Q20        2-chloroethyl 2-chloroethyl                                         Q20        isopropyl     2,2,2-trifluoroethyl                                  Q20        n-propyl      isopropyl                                             Q20        n-propyl      cyclopropyl                                           Q20        isopropyl     isopropyl                                             Q20        isopropyl     phenyl                                                Q20        isopropyl     allyl                                                 Q20        isopropyl     propargyl                                             Q20        allyl         allyl                                                 Q20        propargyl     propargyl                                             Q21        methyl        isopropyl                                             Q21        methyl        cyclopropyl                                           Q21        methyl        cyclohexyl                                            Q21        methyl        1-methyl-2-propenyl                                   Q21        ethyl         ethyl                                                 Q21        ethyl         isopropyl                                             Q21        ethyl         cyclopropyl                                           Q21        ethyl         cyclohexyl                                            Q21        2-chloroethyl isopropyl                                             Q21        2-chloroethyl 2-chloroethyl                                         Q21        isopropyl     2,2,2-trifluoroethyl                                  Q21        n-propyl      isopropyl                                             Q21        n-propyl      cyclopropyl                                           Q21        n-propyl      cyclohexyl                                            Q21        isopropyl     isopropyl                                             Q21        isopropyl     phenyl                                                Q21        isopropyl     allyl                                                 Q21        isopropyl     propargyl                                             Q21        allyl         allyl                                                 Q21        propargyl     propargyl                                             Q22        methyl        isopropyl                                             Q22        ethyl         ethyl                                                 Q22        ethyl         isopropyl                                             Q22        n-propyl      isopropyl                                             Q22        isopropyl     isopropyl                                             Q23        methyl        n-propyl                                              Q23        methyl        isopropyl                                             Q23        methyl        cyclopropyl                                           Q23        methyl        cyclopentyl                                           Q23        methyl        cyclohexyl                                            Q23        methyl        1-methyl-2-propenyl                                   Q23        ethyl         ethyl                                                 Q23        ethyl         n-propyl                                              Q23        ethyl         isopropyl                                             Q23        ethyl         s-butyl                                               Q23        ethyl         phenyl                                                Q23        2-chloroethyl isopropyl                                             Q23        2-chloroethyl 2-chloroethyl                                         Q23        isopropyl     2,2,2-trifluoroethyl                                  Q23        n-propyl      isopropyl                                             Q23        n-propyl      cyclopropyl                                           Q23        n-propyl      cyclopentyl                                           Q23        isopropyl     isopropyl                                             Q23        isopropyl     cyclohexyl                                            Q23        isopropyl     phenyl                                                Q23        isopropyl     allyl                                                 Q23        isopropyl     propargyl                                             Q23        allyl         allyl                                                 Q23        propargyl     propargyl                                             Q24        methyl        ethyl                                                 Q24        methyl        isopropyl                                             Q24        methyl        cyclopropyl                                           Q24        methyl        s-butyl                                               Q24        methyl        phenyl                                                Q24        methyl        1-methyl-2-propenyl                                   Q24        ethyl         ethyl                                                 Q24        ethyl         isopropyl                                             Q24        ethyl         cyclopropyl                                           Q24        ethyl         cyclohexyl                                            Q24        ethyl         2,2,2-trifluoroethyl                                  Q24        n-propyl      2,2,2-trifluoroethyl                                  Q24        isopropyl     2,2,2-trifluoroethyl                                  Q24        2-chloroethyl ethyl                                                 Q24        2-chloroethyl n-propyl                                              Q24        2-chloroethyl isopropyl                                             Q24        2-chloroethyl 2-chloroethyl                                         Q24        n-propyl      isopropyl                                             Q24        n-propyl      s-butyl                                               Q24        n-propyl      cyclohexyl                                            Q24        isopropyl     isopropyl                                             Q24        isopropyl     cyclohexyl                                            Q24        isopropyl     phenyl                                                Q24        isopropyl     allyl                                                 Q24        isopropyl     2-chloro-2-propenyl                                   Q24        isopropyl     2-methyl-2-propenyl                                   Q24        isopropyl     propargyl                                             Q24        allyl         allyl                                                 Q24        propargyl     propargyl                                             Q25        methyl        ethyl                                                 Q25        methyl        isopropyl                                             Q25        methyl        cyclopropyl                                           Q25        methyl        cyclohexyl                                            Q25        methyl        1-methyl-2-propenyl                                   Q25        ethyl         ethyl                                                 Q25        ethyl         isopropyl                                             Q25        ethyl         cyclopropyl                                           Q25        ethyl         cyclohexyl                                            Q25        2-chloroethyl isopropyl                                             Q25        2-chloroethyl 2-chloroethyl                                         Q25        isopropyl     2,2,2-trifluoroethyl                                  Q25        n-propyl      isopropyl                                             Q25        n-propyl      cyclopropyl                                           Q25        isopropyl     isopropyl                                             Q25        isopropyl     phenyl                                                Q25        isopropyl     allyl                                                 Q25        isopropyl     propargyl                                             Q25        allyl         allyl                                                 Q25        propargyl     propargyl                                             Q26        methyl        methyl                                                Q26        methyl        ethyl                                                 Q26        methyl        n-propyl                                              Q26        methyl        isopropyl                                             Q26        methyl        cyclopropyl                                           Q26        methyl        cyclopentyl                                           Q26        methyl        cyclohexyl                                            Q26        methyl        1-methyl-2-propenyl                                   Q26        ethyl         ethyl                                                 Q26        ethyl         isopropyl                                             Q26        ethyl         cyclopropyl                                           Q26        ethyl         cyclohexyl                                            Q26        ethyl         2,2,2-trifluoroethyl                                  Q26        n-propyl      2,2,2-trifluoroethyl                                  Q26        isopropyl     2,2,2-trifluoroethyl                                  Q26        2-chloroethyl ethyl                                                 Q26        2-chloroethyl n-propyl                                              Q26        2-chloroethyl isopropyl                                             Q26        2-chloroethyl 2-chloroethyl                                         Q26        n-propyl      isopropyl                                             Q26        n-propyl      cyclopropyl                                           Q26        isopropyl     isopropyl                                             Q26        isopropyl     phenyl                                                Q26        isopropyl     allyl                                                 Q26        isopropyl     2-chloro-2-propenyl                                   Q26        isopropyl     2-methyl-2-propenyl                                   Q26        isopropyl     propargyl                                             Q26        allyl         allyl                                                 Q26        propargyl     propargyl                                             Q27        methyl        isopropyl                                             Q27        methyl        cyclopropyl                                           Q27        methyl        cyclohexyl                                            Q27        ethyl         ethyl                                                 Q27        ethyl         isopropyl                                             Q27        ethyl         cyclohexyl                                            Q27        n-propyl      isopropyl                                             Q27        isopropyl     isopropyl                                             Q27        isopropyl     phenyl                                                Q28        ethyl         cyclohexyl                                            Q28        ethyl         phenyl                                                Q28        ethyl         2,2,2-trifluoroethyl                                  Q28        n-propyl      2,2,2-trifluoroethyl                                  Q28        isopropyl     2,2,2-trifluoroethyl                                  Q28        2-chloroethyl ethyl                                                 Q28        2-chloroethyl n-propyl                                              Q28        2-chloroethyl isopropyl                                             Q28        2-chloroethyl 2-chloroethyl                                         Q28        n-propyl      isopropyl                                             Q28        n-propyl      cyclopropyl                                           Q28        n-propyl      s-butyl                                               Q28        n-propyl      cyclopentyl                                           Q28        n-propyl      cyclohexyl                                            Q28        isopropyl     isopropyl                                             Q28        isopropyl     cyclohexyl                                            Q28        isopropyl     phenyl                                                Q28        isopropyl     allyl                                                 Q28        isopropyl     2-chloro-2-propenyl                                   Q28        isopropyl     2-methyl-2-propenyl                                   Q28        isopropyl     propargyl                                             Q28        allyl         allyl                                                 Q28        propargyl     propargyl                                             Q29        methyl        methyl                                                Q29        methyl        ethyl                                                 Q29        methyl        n-propyl                                              Q29        methyl        isopropyl                                             Q29        methyl        cyclopropyl                                           Q29        methyl        cyclopentyl                                           Q29        methyl        cyclohexyl                                            Q29        methyl        phenyl                                                Q28        methyl        methyl                                                Q28        methyl        ethyl                                                 Q28        methyl        n-propyl                                              Q28        methyl        isopropyl                                             Q28        methyl        cyclopropyl                                           Q28        methyl        s-butyl                                               Q28        methyl        cyclopentyl                                           Q28        methyl        cyclohexyl                                            Q28        methyl        phenyl                                                Q28        methyl        1-methyl-2-propenyl                                   Q28        ethyl         ethyl                                                 Q28        ethyl         n-propyl                                              Q28        ethyl         isopropyl                                             Q28        ethyl         cyclopropyl                                           Q28        ethyl         s-butyl                                               Q28        ethyl         cyclopentyl                                           Q29        methyl        1-methyl-2-propenyl                                   Q29        ethyl         ethyl                                                 Q29        ethyl         isopropyl                                             Q29        ethyl         cyclopropyl                                           Q29        ethyl         phenyl                                                Q29        ethyl         2,2,2-trifluoroethyl                                  Q29        2-chloroethyl ethyl                                                 Q29        2-chloroethyl n-propyl                                              Q29        2-chloroethyl isopropyl                                             Q29        2-chloroethyl 2-chloroethyl                                         Q29        n-propyl      cyclopropyl                                           Q29        n-propyl      2,2,2-trifluoroethyl                                  Q29        isopropyl     2,2,2-trifluoroethyl                                  Q29        isopropyl     isopropyl                                             Q29        isopropyl     phenyl                                                Q29        isopropyl     allyl                                                 Q29        isopropyl     2-chloro-2-propenyl                                   Q29        isopropyl     2-methyl-2-propenyl                                   Q29        isopropyl     propargyl                                             Q29        allyl         allyl                                                 Q29        propargyl     propargyl                                             Q30        methyl        methyl                                                Q30        methyl        ethyl                                                 Q30        methyl        n-propyl                                              Q30        methyl        isopropyl                                             Q30        methyl        cyclopropyl                                           Q30        methyl        s-butyl                                               Q30        methyl        cyclopentyl                                           Q30        methyl        cyclohexyl                                            Q30        methyl        phenyl                                                Q30        methyl        1-methyl-2-propenyl                                   Q30        ethyl         ethyl                                                 Q30        ethyl         n-propyl                                              Q30        ethyl         isopropyl                                             Q30        ethyl         cyclopropyl                                           Q30        ethyl         s-butyl                                               Q30        ethyl         cyclopentyl                                           Q30        ethyl         cyclohexyl                                            Q30        ethyl         phenyl                                                Q30        ethyl         2,2,2-trifluoroethyl                                  Q30        n-propyl      2,2,2-trifluoroethyl                                  Q30        isopropyl     2,2,2-trifluoroethyl                                  Q30        2-chloroethyl ethyl                                                 Q30        2-chloroethyl n-propyl                                              Q30        2-chloroethyl isopropyl                                             Q30        2-chloroethyl 2-chloroethyl                                         Q30        n-propyl      isopropyl                                             Q30        n-propyl      cyclopropyl                                           Q30        n-propyl      s-butyl                                               Q30        n-propyl      cyclopentyl                                           Q30        n-propyl      cyclohexyl                                            Q30        isopropyl     isopropyl                                             Q30        isopropyl     2-chloro-2-propenyl                                   Q30        isopropyl     2-methyl-2-propenyl                                   Q30        isopropyl     propargyl                                             Q30        isopropyl     cyclohexyl                                            Q30        isopropyl     phenyl                                                Q30        isopropyl     allyl                                                 Q30        allyl         allyl                                                 Q30        propargyl     propargyl                                             Q31        methyl        ethyl                                                 Q31        methyl        n-propyl                                              Q31        methyl        isopropyl                                             Q31        methyl        cyclopropyl                                           Q31        methyl        s-butyl                                               Q31        methyl        1-methyl-2-propenyl                                   Q31        ethyl         ethyl                                                 Q31        ethyl         n-propyl                                              Q31        ethyl         isopropyl                                             Q31        ethyl         cyclopropyl                                           Q31        ethyl         2,2,2-trifluoroethyl                                  Q31        n-propyl      2,2,2-trifluoroethyl                                  Q31        isopropyl     2,2,2-trifluoroethyl                                  Q31        2-chloroethyl ethyl                                                 Q31        2-chloroethyl n-propyl                                              Q31        2-chloroethyl isopropyl                                             Q31        2-chloroethyl 2-chloroethyl                                         Q31        n-propyl      isopropyl                                             Q31        n-propyl      cyclopropyl                                           Q31        isopropyl     isopropyl                                             Q31        isopropyl     phenyl                                                Q31        isopropyl     allyl                                                 Q31        isopropyl     2-chloro-2-propenyl                                   Q31        isopropyl     2-methyl-2-propenyl                                   Q31        isopropyl     propargyl                                             Q31        allyl         allyl                                                 Q31        propargyl     propargyl                                             Q32        methyl        methyl                                                Q32        methyl        ethyl                                                 Q32        methyl        n-propyl                                              Q32        methyl        isopropyl                                             Q32        methyl        cyclopropyl                                           Q32        methyl        s-butyl                                               Q32        methyl        cyclopentyl                                           Q32        methyl        cyclohexyl                                            Q32        methyl        phenyl                                                Q32        methyl        1-methyl-2-propenyl                                   Q32        ethyl         ethyl                                                 Q32        ethyl         n-propyl                                              Q32        ethyl         isopropyl                                             Q32        ethyl         cyclopropyl                                           Q32        ethyl         s-butyl                                               Q32        ethyl         cyclopentyl                                           Q32        ethyl         cyclohexyl                                            Q32        ethyl         phenyl                                                Q32        n-propyl      isopropyl                                             Q32        n-propyl      cyclopropyl                                           Q32        n-propyl      s-butyl                                               Q32        n-propyl      cyclopentyl                                           Q32        n-propyl      cyclohexyl                                            Q32        isopropyl     isopropyl                                             Q32        isopropyl     cyclohexyl                                            Q32        isopropyl     phenyl                                                Q32        isopropyl     allyl                                                 Q32        isopropyl     2-chloro-2-propenyl                                   Q32        isopropyl     2-methyl-2-propenyl                                   Q32        isopropyl     propargyl                                             Q32        allyl         allyl                                                 Q32        propargyl     propargyl                                             Q33        methyl        methyl                                                Q33        methyl        ethyl                                                 Q33        methyl        n-propyl                                              Q33        methyl        isopropyl                                             Q33        methyl        cyclopropyl                                           Q33        methyl        s-butyl                                               Q33        methyl        cyclopentyl                                           Q33        methyl        cyclohexyl                                            Q33        methyl        phenyl                                                Q33        methyl        1-methyl-2-propenyl                                   Q33        ethyl         ethyl                                                 Q33        ethyl         n-propyl                                              Q33        ethyl         isopropyl                                             Q33        ethyl         cyclopropyl                                           Q33        ethyl         s-butyl                                               Q33        ethyl         cyclopentyl                                           Q33        ethyl         cyclohexyl                                            Q33        ethyl         phenyl                                                Q33        ethyl         2,2,2-trifluoroethyl                                  Q33        n-propyl      2,2,2-trifluoroethyl                                  Q33        isopropyl     2,2,2-trifluoroethyl                                  Q33        2-chloroethyl ethyl                                                 Q33        2-chloroethyl n-propyl                                              Q33        2-chloroethyl isopropyl                                             Q33        2-chloroethyl 2-chloroethyl                                         Q33        n-propyl      isopropyl                                             Q33        n-propyl      cyclopropyl                                           Q33        n-propyl      s-butyl                                               Q33        n-propyl      cyclopentyl                                           Q33        n-propyl      cyclohexyl                                            Q33        isopropyl     isopropyl                                             Q33        isopropyl     cyclohexyl                                            Q33        isopropyl     phenyl                                                Q33        isopropyl     allyl                                                 Q33        isopropyl     propargyl                                             Q33        allyl         allyl                                                 Q33        propargyl     propargyl                                             Q34        methyl        n-propyl                                              Q34        methyl        isopropyl                                             Q34        methyl        cyclopropyl                                           Q34        methyl        cyclopentyl                                           Q34        methyl        cyclohexyl                                            Q34        methyl        1-methyl-2-propenyl                                   Q34        ethyl         ethyl                                                 Q34        ethyl         isopropyl                                             Q34        ethyl         cyclopropyl                                           Q34        ethyl         cyclopentyl                                           Q34        ethyl         cyclohexyl                                            Q34        ethyl         2,2,2-trifluoroethyl                                  Q34        n-propyl      2,2,2-trifluoroethyl                                  Q34        isopropyl     2,2,2-trifluoroethyl                                  Q34        2-chloroethyl ethyl                                                 Q34        2-chloroethyl n-propyl                                              Q34        2-chloroethyl isopropyl                                             Q34        2-chloroethyl 2-chloroethyl                                         Q34        n-propyl      isopropyl                                             Q34        n-propyl      cyclopropyl                                           Q34        n-propyl      cyclohexyl                                            Q34        isopropyl     isopropyl                                             Q34        isopropyl     cyclohexyl                                            Q34        isopropyl     phenyl                                                Q34        isopropyl     allyl                                                 Q34        isopropyl     2-chloro-2-propenyl                                   Q34        isopropyl     2-methyl-2-propenyl                                   Q34        isopropyl     propargyl                                             Q34        allyl         allyl                                                 Q34        propargyl     propargyl                                             Q35        methyl        n-propyl                                              Q35        methyl        isopropyl                                             Q35        methyl        cyclopropyl                                           Q35        methyl        s-butyl                                               Q35        methyl        cyclopentyl                                           Q35        methyl        cyclohexyl                                            Q35        methyl        1-methyl-2-propenyl                                   Q35        ethyl         ethyl                                                 Q35        ethyl         isopropyl                                             Q35        ethyl         cyclopropyl                                           Q35        ethyl         cyclopentyl                                           Q35        ethyl         cyclohexyl                                            Q35        ethyl         2,2,2-trifluoroethyl                                  Q35        n-propyl      2,2,2-trifluoroethyl                                  Q35        isopropyl     2,2,2-trifluoroethyl                                  Q35        2-chloroethyl ethyl                                                 Q35        2-chloroethyl n-propyl                                              Q35        2-chloroethyl isopropyl                                             Q35        2-chloroethyl 2-chloroethyl                                         Q35        n-propyl      isopropyl                                             Q35        n-propyl      cyclopropyl                                           Q35        n-propyl      cyclohexyl                                            Q35        isopropyl     isopropyl                                             Q35        isopropyl     cyclohexyl                                            Q35        isopropyl     phenyl                                                Q35        isopropyl     allyl                                                 Q35        isopropyl     2-chloro-2-propenyl                                   Q35        isopropyl     2-methyl-2-propenyl                                   Q35        isopropyl     propargyl                                             Q35        allyl         allyl                                                 Q35        propargyl     propargyl                                             Q36        methyl        methyl                                                Q36        methyl        ethyl                                                 Q36        methyl        n-propyl                                              Q36        methyl        isopropyl                                             Q36        methyl        cyclopropyl                                           Q36        methyl        s-butyl                                               Q36        methyl        cyclopentyl                                           Q36        methyl        cyclohexyl                                            Q36        methyl        phenyl                                                Q36        methyl        1-methyl-2-propenyl                                   Q36        ethyl         ethyl                                                 Q36        ethyl         n-propyl                                              Q36        ethyl         isopropyl                                             Q36        ethyl         cyclopropyl                                           Q36        ethyl         s-butyl                                               Q36        ethyl         cyclopentyl                                           Q36        ethyl         cyclohexyl                                            Q36        ethyl         phenyl                                                Q36        ethyl         2,2,2-trifluoroethyl                                  Q36        n-propyl      2,2,2-trifluoroethyl                                  Q36        isopropyl     2,2,2-trifluoroethyl                                  Q36        2-chloroethyl ethyl                                                 Q36        2-chloroethyl n-propyl                                              Q36        2-chloroethyl isopropyl                                             Q36        2-chloroethyl 2-chloroethyl                                         Q36        n-propyl      isopropyl                                             Q36        n-propyl      cyclopropyl                                           Q36        n-propyl      s-butyl                                               Q36        n-propyl      cyclopentyl                                           Q36        n-propyl      cyclohexyl                                            Q36        isopropyl     isopropyl                                             Q36        isopropyl     cyclohexyl                                            Q36        isopropyl     phenyl                                                Q36        isopropyl     allyl                                                 Q36        isopropyl     2-chloro-2-propenyl                                   Q36        isopropyl     2-chloro-2-propenyl                                   Q36        isopropyl     propargyl                                             Q36        allyl         allyl                                                 Q36        propargyl     propargyl                                             Q37        methyl        methyl                                                Q37        methyl        ethyl                                                 Q37        methyl        n-propyl                                              Q37        methyl        isopropyl                                             Q37        methyl        cyclopropyl                                           Q37        methyl        s-butyl                                               Q37        methyl        cyclopentyl                                           Q37        methyl        cyclohexyl                                            Q37        methyl        phenyl                                                Q37        methyl        1-methyl-2-propenyl                                   Q37        ethyl         ethyl                                                 Q37        ethyl         n-propyl                                              Q37        ethyl         isopropyl                                             Q37        ethyl         cyclopropyl                                           Q37        ethyl         s-butyl                                               Q37        ethyl         cyclopentyl                                           Q37        ethyl         cyclohexyl                                            Q37        ethyl         phenyl                                                Q37        ethyl         2,2,2-trifluoroethyl                                  Q37        n-propyl      2,2,2-trifluoroethyl                                  Q37        isopropyl     2,2,2-trifluoroethyl                                  Q37        2-chloroethyl ethyl                                                 Q37        2-chloroethyl n-propyl                                              Q37        2-chloroethyl isopropyl                                             Q37        2-chloroethyl 2-chloroethyl                                         Q37        n-propyl      isopropyl                                             Q37        n-propyl      cyclopropyl                                           Q37        n-propyl      s-butyl                                               Q37        n-propyl      cyclopentyl                                           Q37        n-propyl      cyclohexyl                                            Q37        isopropyl     isopropyl                                             Q37        isopropyl     cyclohexyl                                            Q37        isopropyl     phenyl                                                Q37        isopropyl     allyl                                                 Q37        isopropyl     2-chloro-2-propenyl                                   Q37        isopropyl     2-methyl-2-propenyl                                   Q37        isopropyl     propargyl                                             Q37        allyl         allyl                                                 Q37        propargyl     propargyl                                             Q38        methyl        methyl                                                Q38        methyl        ethyl                                                 Q38        methyl        n-propyl                                              Q38        methyl        isopropyl                                             Q38        methyl        cyclopropyl                                           Q38        methyl        s-butyl                                               Q38        methyl        cyclopentyl                                           Q38        methyl        cyclohexyl                                            Q38        methyl        phenyl                                                Q38        methyl        1-methyl-2-propenyl                                   Q38        ethyl         ethyl                                                 Q38        ethyl         n-propyl                                              Q38        ethyl         isopropyl                                             Q38        ethyl         cyclopropyl                                           Q38        ethyl         s-butyl                                               Q38        ethyl         cyclopentyl                                           Q38        ethyl         cyclohexyl                                            Q38        ethyl         phenyl                                                Q38        ethyl         2,2,2-trifluoroethyl                                  Q38        n-propyl      2,2,2-trifluoroethyl                                  Q38        isopropyl     2,2,2-trifluoroethyl                                  Q38        2-chloroethyl ethyl                                                 Q38        2-chloroethyl n-propyl                                              Q38        2-chloroethyl isopropyl                                             Q38        2-chloroethyl 2-chloroethyl                                         Q38        n-propyl      isopropyl                                             Q38        n-propyl      cyclopropyl                                           Q38        n-propyl      s-butyl                                               Q38        n-propyl      cyclopentyl                                           Q38        n-propyl      cyclohexyl                                            Q38        isopropyl     isopropyl                                             Q38        isopropyl     cyclohexyl                                            Q38        isopropyl     phenyl                                                Q38        isopropyl     allyl                                                 Q38        isopropyl     2-chloro-2-propenyl                                   Q38        isopropyl     2-methyl-2-propenyl                                   Q38        isopropyl     propargyl                                             Q38        allyl         allyl                                                 Q38        propargyl     propargyl                                             Q39        methyl        isopropyl                                             Q39        methyl        cyclopropyl                                           Q39        ethyl         ethyl                                                 Q39        ethyl         isopropyl                                             Q39        ethyl         cyclopropyl                                           Q39        n-propyl      isopropyl                                             Q39        isopropyl     isopropyl                                             Q39        isopropyl     phenyl                                                Q40        methyl        ethyl                                                 Q40        methyl        isopropyl                                             Q40        methyl        cyclopropyl                                           Q40        methyl        1-methyl-2-propenyl                                   Q40        ethyl         ethyl                                                 Q40        ethyl         isopropyl                                             Q40        ethyl         cyclopropyl                                           Q40        ethyl         cyclohexyl                                            Q40        n-propyl      isopropyl                                             Q40        n-propyl      cyclopropyl                                           Q40        n-propyl      cyclohexyl                                            Q40        isopropyl     isopropyl                                             Q40        isopropyl     phenyl                                                Q40        isopropyl     allyl                                                 Q41        methyl        methyl                                                Q41        methyl        ethyl                                                 Q41        methyl        n-propyl                                              Q41        methyl        isopropyl                                             Q41        methyl        cyclopropyl                                           Q41        methyl        s-butyl                                               Q41        methyl        cyclopentyl                                           Q41        methyl        cyclohexyl                                            Q41        methyl        phenyl                                                Q41        methyl        1-methyl-2-propenyl                                   Q41        ethyl         ethyl                                                 Q41        ethyl         n-propyl                                              Q41        ethyl         isopropyl                                             Q41        ethyl         cyclopropyl                                           Q41        ethyl         s-butyl                                               Q41        ethyl         cyclopentyl                                           Q41        ethyl         cyclohexyl                                            Q41        ethyl         phenyl                                                Q41        n-propyl      isopropyl                                             Q41        n-propyl      cyclopropyl                                           Q41        n-propyl      s-butyl                                               Q41        n-propyl      cyclopentyl                                           Q41        n-propyl      cyclohexyl                                            Q41        isopropyl     isopropyl                                             Q41        isopropyl     cyclohexyl                                            Q41        isopropyl     phenyl                                                Q41        isopropyl     allyl                                                 Q41        isopropyl     2-chloro-2-propenyl                                   Q41        isopropyl     2-methyl-2-propenyl                                   Q41        isopropyl     propargyl                                             Q41        allyl         allyl                                                 Q41        propargyl     propargyl                                             ______________________________________                                    

                  TABLE 2                                                          ______________________________________                                          ##STR6##                                                                                   ##STR7##                                                          ______________________________________                                         Q1          pyrrolidinyl                                                       Q1          piperidyl                                                          Q2          piperidyl                                                          Q2          morpholinyl                                                        Q3          pyrrolidinyl                                                       Q3          morpholinyl                                                        Q4          pyrrolidinyl                                                       Q4          piperidyl                                                          Q4          morpholinyl                                                        Q4          2-methylpiperidyl                                                  Q5          pyrrolidinyl                                                       Q5          piperidyl                                                          Q5          morpholinyl                                                        Q5          2-methyl-1,2,3,4-tetrahydroquinolyl                                Q5          2,5-dimethylpyrrolidinyl                                           Q5          2,5-dimethyl-3-pyrrolinyl                                          Q5          2,6-dimethylpiperidyl                                              Q6          pyrrolidinyl                                                       Q6          piperidyl                                                          Q6          morpholinyl                                                        Q6          2,5-dimethylpyrrolidinyl                                           Q7          pyrrolidinyl                                                       Q7          piperidyl                                                          Q7          morpholinyl                                                        Q8          pyrrolidinyl                                                       Q8          piperidyl                                                          Q8          morpholinyl                                                        Q8          2-methylpiperidyl                                                  Q8          2,5-dimethylpyrrolidinyl                                           Q8          2,5-dimethyl-3-pyrrolinyl                                          Q8          2,6-dimethylpiperidyl                                              Q9          pyrrolidinyl                                                       Q9          piperidyl                                                          Q9          morpholinyl                                                        Q9          2,6-dimethylpiperidyl                                              Q10         pyrrolidinyl                                                       Q10         piperidyl                                                          Q10         morpholinyl                                                        Q11         pyrrolidinyl                                                       Q11         piperidyl                                                          Q11         morpholinyl                                                        Q12         pyrrolidinyl                                                       Q12         piperidyl                                                          Q12         morpholinyl                                                        Q13         pyrrolidinyl                                                       Q13         piperidyl                                                          Q13         morpholinyl                                                        Q14         pyrrolidinyl                                                       Q14         piperidyl                                                          Q14         morpholinyl                                                        Q14         2-methylpiperidyl                                                  Q14         2,5-dimethylpyrrolidinyl                                           Q14         2,5-dimethyl-3-pyrrolinyl                                          Q14         2,6-dimethylpiperidyl                                              Q15         pyrrolidinyl                                                       Q15         piperidyl                                                          Q15         morpholinyl                                                        Q15         2,6-dimethylpiperidyl                                              Q16         pyrrolidinyl                                                       Q16         piperidyl                                                          Q16         morpholinyl                                                        Q17         pyrrolidinyl                                                       Q17         piperidyl                                                          Q17         morpholinyl                                                        Q18         pyrrolidinyl                                                       Q18         piperidyl                                                          Q18         morpholinyl                                                        Q18         2,6-dimethylpiperidyl                                              Q19         pyrrolidinyl                                                       Q19         piperidyl                                                          Q19         morpholinyl                                                        Q19         2,5-dimethylpyrrolidinyl                                           Q19         2,5-dimethyl-3-pyrrolinyl                                          Q19         2,6-dimethylpiperidyl                                              Q20         pyrrolidinyl                                                       Q20         piperidyl                                                          Q20         morpholinyl                                                        Q20         2-methyl-1,2,3,4-tetrahydroquinolyl                                Q21         pyrrolidinyl                                                       Q21         piperidyl                                                          Q21         morpholinyl                                                        Q21         2-methylpiperidyl                                                  Q22         pyrrolidinyl                                                       Q22         piperidyl                                                          Q23         pyrrolidinyl                                                       Q23         piperidyl                                                          Q23         morpholinyl                                                        Q23         2,5-dimethylpyrrolidinyl                                           Q23         2,6-dimethylpiperidyl                                              Q24         pyrrolidinyl                                                       Q24         piperidyl                                                          Q24         morpholinyl                                                        Q24         2-methylpiperidyl                                                  Q24         2,5-dimethylpyrrolidinyl                                           Q24         2,5-dimethyl-3-pyrrolinyl                                          Q24         2,6-dimethylpiperidyl                                              Q25         pyrrolidinyl                                                       Q25         piperidyl                                                          Q25         morpholinyl                                                        Q25         2,5-dimethylpyrrolidinyl                                           Q25         2,6-dimethylpiperidyl                                              Q26         pyrrolidinyl                                                       Q26         piperidyl                                                          Q26         morpholinyl                                                        Q26         2,5-dimethylpyrrolidinyl                                           Q26         2,6-dimethylpiperidyl                                              Q26         2,5-dimethyl-3-pyrrolinyl                                          Q27         pyrrolidinyl                                                       Q27         piperidyl                                                          Q28         pyrrolidinyl                                                       Q28         piperidyl                                                          Q28         morpholinyl                                                        Q28         2-methylpiperidyl                                                  Q28         2,5-dimethylpyrrolidinyl                                           Q28         2,6-dimethylpiperidyl                                              Q28         2-methyl-1,2,3,4-tetrahydroquinolyl                                Q28         2,5-dimethyl-3-pyrrolinyl                                          Q29         pyrrolidinyl                                                       Q29         piperidyl                                                          Q29         morpholinyl                                                        Q29         2,5-dimethylpyrrolidinyl                                           Q29         2,5-dimethyl-3-pyrrolinyl                                          Q29         2,6-dimethylpiperidyl                                              Q30         pyrrolidinyl                                                       Q30         piperidyl                                                          Q30         morpholinyl                                                        Q30         2-methylpiperidyl                                                  Q30         2,5-dimethylpyrrolidinyl                                           Q30         2,5-dimethyl-3-pyrrolinyl                                          Q30         2,6-dimethylpiperidyl                                              Q30         2-methyl-1,2,3,4-tetrahydroquinolyl                                Q31         pyrrolidinyl                                                       Q31         piperidyl                                                          Q31         morpholinyl                                                        Q32         pyrrolidinyl                                                       Q32         piperidyl                                                          Q32         morpholinyl                                                        Q32         2-methylpiperidyl                                                  Q32         2,5-dimethylpyrrolidinyl                                           Q32         2,6-dimethylpiperidyl                                              Q32         2-methyl-1,2,3,4-tetrahydroquinolyl                                Q33         pyrrolidinyl                                                       Q33         piperidyl                                                          Q33         2,6-dimethylpiperidyl                                              Q33         morpholinyl                                                        Q33         2-methylpiperidyl                                                  Q33         2,5-dimethylpyrrolidinyl                                           Q33         2,6-dimethylpiperidyl                                              Q33         2-methyl-1,2,3,4-tetrahydroquinolyl                                Q34         pyrrolidinyl                                                       Q34         piperidyl                                                          Q34         morpholinyl                                                        Q34         2,5-dimethylpyrrolidinyl                                           Q34         2,5-dimethyl-3-pyrrolinyl                                          Q34         2,6-dimethylpiperidyl                                              Q35         pyrrolidinyl                                                       Q35         piperidyl                                                          Q35         morpholinyl                                                        Q35         2,5-dimethylpyrrolidinyl                                           Q35         2,5-dimethyl-3-pyrrolinyl                                          Q35         2,6-dimethylpiperidyl                                              Q36         pyrrolidinyl                                                       Q36         piperidyl                                                          Q36         morpholinyl                                                        Q36         2-methylpiperidyl                                                  Q36         2,5-dimethylpyrrolidinyl                                           Q36         2,5-dimethyl-3-pyrrolinyl                                          Q36         2,6-dimethylpiperidyl                                              Q36         2-methyl-1,2,3,4-tetrahydroquinolyl                                Q37         pyrrolidinyl                                                       Q37         piperidyl                                                          Q37         morpholinyl                                                        Q37         2-methylpiperidyl                                                  Q37         2,5-dimethyl-3-pyrrolinyl                                          Q37         2,5-dimethylpyrrolidinyl                                           Q37         2,6-dimethylpiperidyl                                              Q37         2-methyl-1,2,3,4-tetrahydroquinolyl                                Q38         pyrrolidinyl                                                       Q38         piperidyl                                                          Q38         morpholinyl                                                        Q38         2,6-dimethylpiperidyl                                              Q38         2-methylpiperidyl                                                  Q38         2,5-dimethylpyrrolidinyl                                           Q38         2,5-dimethyl-3-pyrrolinyl                                          Q38         2-methyl-1,2,3,4-tetrahydroquinolyl                                Q39         pyrrolidinyl                                                       Q39         piperidyl                                                          Q39         morpholinyl                                                        Q40         pyrrolidinyl                                                       Q40         piperidyl                                                          Q40         morpholinyl                                                        Q40         2-methyl-1,2,3,4-tetrahydroquinolyl                                Q41         pyrrolidinyl                                                       Q41         piperidyl                                                          Q41         morpholinyl                                                        Q41         2,5-dimethylpyrrolidinyl                                           ______________________________________                                    

When in the process (a), for example, 1-(2-chloro-3-pyridyl)-5(4H)-tetrazolinone and diethylcarbamoyl chloride are used as starting materials, the course of the reaction can be represented by the following equation: ##STR8##

In the process (a), the starting materials of the formula (II) mean those based on the above definition of R³ and n, and preferably those based on the above preferred definitions.

The compounds of the formula (II) are novel, and can be obtained when (b) compounds of the formula (IV) ##STR9## wherein R³ and n have the same meanings as mentioned above, are reacted with trimethylsilylazide (at least 2 mols) and then with water or--preferably--with methanol, or (c) compounds of the formula (V) ##STR10## wherein R³ and n have the stone meanings as mentioned above, are reacted first with trimethylsilylazide and then with water or--preferably--with methanol, or (d) compounds of the formula (VI) ##STR11## wherein R³ and n have the stone meanings as mentioned above, are reacted with an inorganic base (optionally in aqueous solution), in the presence of inert solvents, and if appropriate, in the presence of acid binders, or (e) compounds of the formula (VII) ##STR12## wherein R³ and n have the same meanings as mentioned above, are reacted with sodium azide, in the presence of anhydrous aluminum chloride and in the presence of inert solvents.

The compounds of the formula (IV) are well known compounds in the field of organic chemistry (being sold generally as a reagent). The following compounds, are illustrative:

picolinic acid chloride,

nicotinic acid chloride,

isonicotinic acid chloride,

2-methylthio nicotinic acid chloride, and

2,6-dichloroisonicotinic acid chloride.

The compounds of the formula (IV) can easily be obtained by chlorinating, in a usual manner, the compounds represented by the formula (VIII) ##STR13## wherein R³ and n have the same meanings as mentioned above.

The preferred compounds of the formula (VIII) are those wherein R³ and n have the preferred definitions set forth hereinabove.

The compounds of the formula (VIII) are well known compounds in the field of organic chemistry. For example, said compounds may be synthesized by the processes described in WO 93/8005, French Patent Laid-Open 2686340, EP-A 166907, 181311, 55011, Japanese Patent Laid-Open Application Hei 3-81263, Journal of the Chemical Society of London, vol. 67, page 407, vol. 73, page 590, Journal of Organic Chemistry, vol. 19, page 1633, 1954, Tetrahedron, vol. 50(No. 4), pages 1129-1134, 1994, Bulletin de la Societe Chimiqque de France, (3-4, Pt.2), pages 530-532, 1976, Applied Radiation. Isotopes, vol. 42 (No. 3), pages 215-220, 1991, Chemisch Berichte, vol. 14, page 645, 1881, vol. 19, page 1305, 1886, vol. 35, page 1352, 1902, vol. 61, page 2202, 1928, Journal of Chemical Research, Synopsis, (1), pages 20-21, 1986, Journal of Pharmacie de Belgique, vol. 35(No. 2), pages 98-102, 1980, or by processes similar thereto, some sold as reagents. The following compounds, for example, are illustrative:

picolinic acid,

nicotinic acid,

isonicotinic acid,

2-chloronicotinic acid,

6-chloronicotinic acid,

2-methylnicotinic acid,

2-methoxynicotinic acid,

4-trifluoromethylnicotinic acid,

2,6-dichloronicotinic acid,

2-chloro-6-methylnicotinic acid,

4-fluoronicotinic acid,

4-chloronicotinic acid,

3-fluoroisonicotinic acid,

3-bromoisonicotinic acid,

2-chloroisonicotinic acid,

3-chloroisonicitinic acid,

4-methylnicotinic acid,

3-methylisonicotinic acid,

3-methylthioisonicotinic acid,

2-trifluoromethylnicotinic acid,

3,5-dichloroisonicotinic acid,

2-chloro-4-methylnicoticic acid,

2,6-dimethylnicoticinic acid,

2,4-dimethylnicotinic acid,

4-ethylnicotinic acid,

2-methylthionicotinic acid,

5-trifluoromethoxypicolicinc acid,

2-chloro-4,6-dimethylnicotinic acid,

6-chloro-2,4-dimethylnicotinic acid,

5-tricluoromethoxypicolinic acid, and

4,6-dimethoxy-2-trifluoromethylnicotinic acid.

The reaction of the above-mentioned process (b) can be carried out in a similar manner to the synthesis of tetrazolinones described in Journal of Chemical Society, Perkin Transaction 1, 1992, pages 1101-1104, or The Journal of American Chemical Society, Vol. 81, 1959, pages 3076-3079.

In the process (c) according to the invention, the preferred starting compounds of the formula (V) are those based on the above preferred definition of R¹ and n.

The compounds of the formula (V) are well known compounds in the field of organic chemistry, for example, 2,6-dichloro-4-pyridyl isocyanate. Said compounds can also easily be obtained by Curtius rearrangement of the compounds of the above mentioned formula (IV) or by Schmidt rearrangement of compounds of the above-mentioned formula (VIII).

The reaction of the above-mentioned process (c) can be carried out in a similar manner to the synthesis of tetrazolinones described in The Journal of Organic Chemistry, Vol. 45, 1980, pages 5130 -5136 or The Journal of American Chemical Society, vol. 81, 1959, pages 3076-3079.

In the above-mentioned process (d), preferred starting compounds of the formula (VI) are those based on the above preferred definitions of R¹ and n.

The compounds of the formula (VI) can easily be prepared by the following process (f): (f) compounds of the following formula(IX) ##STR14## wherein R³ and n have the same meanings as mentioned above are reacted with oxidizing agents, in the presence of inert solvents.

In the above-mentioned process (f), the preferred starting compounds of the formula (IX) are those based on the above preferred definitions of R¹ and n.

In the above-mentioned process (f), the oxidizing agents preferably have a suitable oxidative effect such that one nitrogen atom of the pyridine ring is not oxidized. As examples of said oxidizing agent, there may be mentioned: OXONE® potassium permanganate, potassium hydrogen persulfate, ruthenium oxide, osmium oxide, sodium metapedodate, dinitrogen tetroxide, hydrogen peroxide, peracid, hydroperoxide and ozone. When hydrogen peroxide is used as oxidizing agent, it is advantageous to use a tungsten catalyst such as sodium tungstate.

The compounds of the formula (IX) can easily be prepared by the following process (g): (g) compounds of the following formula (X) ##STR15## wherein R³ and n have the same meanings mentioned above, are reacted with dimethyl sulfate and then, under acid conditions, the resulting products are reacted with sodium nitrite or potassium nitrite.

The reaction of the process (g) can be carried out in a manner similar to the synthesis of tetrazolinones described in Chemische Berichte vol. 34, page 3115, 1901.

In the above-mentioned process (g), the preferred starting compounds of the formula (X) are those based on the above preferred definitions of R¹ and n.

The compounds of the formula (X) can be obtained by the following known process (h): (h) compounds of the following formula (XI) ##STR16## wherein R³ and n have the same meaning mentioned above, are reacted with hydrazine.

In the reaction of the process (h), the preferred starting compounds of the formula (XI) are those based on the above preferred definitions of R¹ and n.

The compounds of the formula (XI) can be obtained by the following process (i): (i) compounds of the following formula (XII) ##STR17## wherein R³ and n have the same meanings mentioned above, are reacted with methyliodide.

In the reaction of the process (i), the starting compounds of the formula (XII) mean those based on the above definitions of R³ and n, and preferably based on the above preferred definitions.

The compounds of the formula (XII) can be obtained by the following process (j): (j) aminopyridines of the following formula (XlII) ##STR18## wherein R³ and n have the same meanings mentioned above, are reacted with carbon disulfide, in the presence of tertiary amines such as triethyl amine, and if appropriate in the presence of inert solvents.

In the reaction of the process (j), the starting compounds of the formula (XIII) mean those based on the above definitions of R³ and n, and preferably based on the above preferred definitions.

In the reactions of the processes (i) and (j) can be carried out in a similar manner to the method of preparing tetrazolinones described in Journal of the Chemical Society, pages 796-802, 1955 or pages 1644-1649, 1956 The compounds of the formula (XIII) are well known compounds in the field of organic chemistry. For example, said compounds may be synthesized by the processes described in Recueil des Travaux Chimiques des Pays. Bas, vol. 69, pages 673, 1950, The Journal of American Chemical Society, vol. 69, page 63, 1947, vol. 69, page 69, 1947, vol, 73 pages 5043-5046, 1951, The Journal of Organic Chemistry, vol. 19, page 1633, 1954 or by processes similar thereto, or are commercially available. As examples of said compounds, there may he mentioned:

2-aminopyridine,

3-aminopyridine,

4-aminopyridine,

2-amino-3-chloropyridine,

2-amino-3-methylpyridine,

3-amino-2-methylpyridine,

4-amino-3-methylpyridine,

2-amino-3-methoxypyridine,

2-amino-3,5-dichloropyridine,

4-amino-2,6-dichloropyridine, and

2-amino-3-chloro-5-trifluoromethylpyridine.

The compounds of the formula (XIII) can be obtained by the following known process (k): (k) chloropyridines of the formula (XIV) ##STR19## wherein R³ and n have the same meanings mentioned above, are aminated.

The above-mentioned process (k) can be carried out similarly to that described in, for example, Heterocycles vol. 26, pages 2065-2068, 1987, Vol. 22, pages 117-124, 1984, or Japanese Patent Laid-Open Application Sho 62-155260.

In the reaction of the process (k), the starting compounds of the formula (XIV) mean those based on the above definitions of R³ and n, and preferably based on the above preferred definitions.

Chloropyridines represented by the formula (XIV) are well known compounds in the field of organic chemistry, being sold as reagents, and for example there may be mentioned:

2-chloro-3-trifluoromethylpyridine,

2-chloro-5-trifluoromethylpyridine, and

2-chloro-3,5-ditrifluoromethylpyridine.

In the process (d), as examples of the inorganic bases, there may be mentioned:

sodium hydroxide,

potassium hydroxide,

sodium carbonate,

potassium carbonate,

sodium bicarbonate, and

potassium bicarbonate.

In the reaction of the process (e), the starting compounds of the formula (VII) mean those based on the above definitions of R³ and n, and preferably based on the above preferred definitions.

The compounds of the formula (VII) can easily be obtained by the following known process (I): (I) aminopyridines represented by the above-mentioned formula (XIII) are reacted with phenylchloroformate, if appropriate in the presence of inert solvents.

In carrying out the process (e) mentioned above, use may be made, as suitable diluent, of any inert solvent.

Examples of such diluents are aliphatic, cycloaliphatic and aromatic, optionally chlorinated, hydrocarbons such as toluene, xylene, chlorobenzene, dichlorobenzene, and the like; ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofurane (THF), dimethylene glycol, dimethyl ether (DGM) and the like; acid amides such as dimethyl formamide (DMF), dimethyl acetamide (DMA), N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide (HMPA), and the like; sulfones and sulfoxides such as dimethyl sulfoxide (DMSO), sulfolane and the like.

In the above mentioned process (e), the reaction temperature can be varied within a substantially wide range. In general, the reaction is carried out at a temperature of from about 0° C. to about 200° C., preferably from 20° C. to about 150° C.

Further, the reaction is carried out under normal pressure, although it is also possible to employ a higher or reduced pressure.

When the above mentioned process (e) according to the present invention is carried out, use is made, for example, of about 1 to 3 mols of sodium azide in a diluent such as dimethyl formamide per mol of the compounds represented by the general formula (VII) to obtain the desired compounds.

As specific examples of the formula (II), in the above-mentioned process (a), there may be mentioned:

1-(2-chloro-3-pyridyl)-5(4H)-tetrazolinone,

1-(2-chloro-4-pyridyl)-5(4H)-tetrazolinone,

1-(2-pyridyl)-5(4H)-tetrazolinone,

1-(3-pyridyl)-5(4H)-tetrazolinone,

1-(4-pyridyl)-5(4H)-tetrazolinone,

1-(3-chloro-2-pyridyl)-5(4H)-tetrazolinone,

1-(4-fluoro-3-pyridyl)-5 (4H)-tetrazolinone,

1-(3-chloro-4-pyridyl)-5(4H)-tetrazolinone,

1-(3-bromo-4-pyridyl)-5(4H)-tetrazolinone,

1-(6-chloro-3-pyridyl)-5(4H)-tetrazolinone,

1-(3-methyl-2-pyridyl)-5(4H)-tetrazolinone,

1-(3-fluoro-4-pyridyl)-5(4H)-tetrazolinone,

1-(2-methyl-3-pyridyl)-5(4H)-tetrazolinone,

1-(4-chloro-3-pyridyl)-5(4H)-tetrazolinone,

1-(3-methoxy-2-pyridyl)-5(4H)-tetrazolinone,

1-(4-methyl-3-pyridyl)-5(4H)-tetrazolinone,

1-(2-methylthio-3-pyridyl)-5(4H)-tetrazolinone,

1-(3-methyl-4-pyridyl)-5(4H)-tetrazolinone,

1-(2-trifluoromethyl-3-pyridyl)-5(4H)-tetrazolinone,

1-(2,6-dichloro-3-pyridyl)-5(4H)-tetrazolinone,

1-(3-trifluoromethyl-2-pyridyl)-5(4H)-tetrazolinone,

1-(2-chloro-6-methyl-3-pyridyl)-5(4H)-tetrazolinone,

1 -(2-methoxy-3-pyridyl)-5(4H)-tetrazolinone,

1 -(2,6-dichloro-4-pyridyl)-5(4H)-tetrazolinone,

1 -(4-trifluoromethyl-3-pyridyl)-5(4H)-tetrazolinone,

1 - (3,5-dichloro-2-pyridyl)-5(4H)-tetrazolinone,

1-(3-methylthio-4-pyridyl)-5(4H)-tetrazolinone,

1-(5-trifluoromethyl-2-pyridyl)-5(4H)-tetrazolinone,

1-(3,5-dichloro-4-pyridyl)-5(4H)-tetrazolinone,

1-(2-chloro-4-methyl-3-pyridyl)-5(4H)-tetrazolinone,

1-(3-chloro-5-trifluoromethyl-2-pyridyl)-5(4H)-tetrazolinone,

1 -(4,6-dimethoxy-2-trifluoromethyl-3-pyridyl)-5(4H)-tetrazolinone,

1-(2,6-dimethyl-3-pyridyl)-5(4H)-tetrazolinone,

1 -(6-chloro-2,4-dimethyl-3-pyridyl)-5(4H)-tetrazolinone,

1 -(3-ethyl-pyridyl)-5(4H)-tetrazolinone,

1-(2-chloro-4,6-dimethyl-3-pyridyl)-5(4H)-tetrazolinone,

1-(5-trifluoromethoxy-2-pyridyl)-5(4H)-tetrazolinone,

1-(2,4-dimethyl-3-pyridyl)-5(4H)-tetrazolinone,

1 -(3-nitro-2-pyridyl-pyridyl)-5(4H)-tetrazolinone,

1-(3,5-bis(trifluoromethyl)-2-pyridyl)-5(4H)-tetrazolinone, and

1-(2-phenoxy-3-pyridyl)-5(4H)-tetrazolinone.

In the process (a), the starling materials of the formula (III) means those based on the above mentioned definition of R¹ and R², and preferably compounds based on the above preferred definitions.

The compounds of the formula (III) are well known in the field of organic chemistry.

As examples of the compounds of the formula (III), the following compounds may be mentioned:

Diisopropylcarbamoyl chloride and bromide,

Diethylcarbamoyl chloride and bromide,

Dimethylcarbamoyl chloride and bromide,

N-methyl-N-ethylcarbamoyl chloride and bromide,

N-methyl-N-n-propylcarbamoyl chloride and bromide,

N-methyl-N-isopropylcarbamoyl chloride and bromide,

N-methyl-N-cyclopropylcarbamoyl chloride and bromide,

N-methyl-N-s-butylcarbamoyl chloride and bromide.

N-methyl-N-cyclopenthylcarbamoyl chloride and bromide,

N-methyl-N-cyclohexylcarbamoyl chloride and bromide,

N-methyl-N-phenylcarbamoyl chloride and bromide,

N-methyl-N-1-methyl-2-propenylcarbamoyl chloride and bromide,

N-ethyl-N-propylcarbamoyl chloride and bromide,

N-ethyl-N-isopropylcarbamoyl chloride and bromide,

N-ethyl-N-cyclopropylcarbamoyl chloride and bromide,

N-ethyl-N-s-butylcarbamoyl chloride and bromide,

N-ethyl-N-cyclopentylcarbamoyl chloride and bromide,

N-ethyl-N-cyclohexylcarbamoyl chloride and bromide,

N-ethyl-N-phenylcarbamoyl chloride and bromide,

N-n-propyl-N-isopropylcarbamoyl chloride and bromide,

N-n-propyl-N-cyclopropylcarbamoyl chloride and bromide,

N-n-propyl-N-s-butylcarbamoyl chloride and bromide,

N-n-propyl-N-cyclopentylcarbamoyl chloride and bromide,

N-n-propyl-N-cyclohexylcarbamoyl chloride and bromide,

N-isopropyl-N-cyclohexylcarbamoyl chloride and bromide,

N-isopropyl-N-phenylcarbamoyl chloride and bromide,

N-isopropyl-N-allylcarbamoyl chloride and bromide,

4-morpholinylcarbamoyl chloride add bromide,

1-(2-methylpiperidine)carbamoyl chloride and bromide,

1-(2,5-dimethylpyrrolidine)carbamoyl chloride and bromide,

1-(2,6-dimethylpiperidine)carbamoyl chloride and bromide,

1-(2-methyl-1,2,3,4-tetrahydroquinoline)carbamoyl chloride and bromide,

1-Pyrrolidinylcarbamoyl chloride and bromide,

1-Piperidylacrbamoyl chloeide and bromide, and

1-(2,5-dimethyl-3-pyrroline)carbamoyl and bromide.

In carrying out the process (a) mentioned above, use may be made, as suitable diluent, of any inert solvent.

Examples of such diluents are aliphatic, cycloaliphatic and aromatic, optionally chlorinated, hydrocarbons such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, and the like; ethers such as diethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, dioxane, dimethoxyethane(DME), tetrahydrofurane (THF) dimethylene glycol dimethyl ether and the like; nitriles such as acetonitrile, propionitrile, and the like; acid amides such as dimethyl formamide (DMF), dimethyl acetamide (DMA), N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide (HMPA),and the like; sulfones and sulfoxides such as dimethyl sulfoxide (DMSO), sulfolane and the like; and bases such as pyridine.

The process (a) according to the invention is carried out preferably in the presence of acid or acid binder.

As examples of such acid binder there may be mentioned: inorganic bases including hydroxide, carbonate, bicarbonate and alcoholate of alkali metals such as, for example, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, and the like, inorganic, alkal metal amide including lithium amide, sodium amide, potassium amide, and the like organic bases including tertiary amines, dialkylaminoanilines and pyridines such as, for example, triethylamine, tributylamine, 1,1,4,4-tetra-methylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP), 1,4-diaza-bicyclo-[2,2,2]octane (DABCO), 1,8-diaza-bicyclo[5,4,0]-undec-7-ene (DBU) and the like, organic lithium compounds including methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, dimethyl copper lithium, lithiumdiisopropylamide, lithiumcyclohexylisopropylamide, lithiumdicyclohexylamide, n-butyllithium DABCO n-butyllithium TMEDA,

In the above mentioned process (a), the reaction temperature can be varied within a substantially wide range. In general, the reaction is carried out at a temperature of from about -30° C. to about 200° C., preferably from -200° C. to about 130° C.

Further, the reaction is carried out under normal pressure, although it is also possible to employ a higher or reduced pressure.

When the above mentioned process (a) according to the present invention is carried out, use is made, for example, of about 1.0 to 1.5 mols of the compound of the formula (III) in a diluent such as toluene per mol of the compounds represented by the general formula (II) in the presence of 1 to 1.5 mols of the acid binder to obtain the desired compounds.

The active compounds according to the invention can be used as defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weedkillers.

By weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, for example, in connection with the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricada, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver and Centaurea.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeurn, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.

However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.

The compounds are suitable, depending on the concentration, for the total combating of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for combating weeds in perennial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, and for the selective combating of weeds in annual cultures.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, foams, pastes, granules, tablets, aerosols, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances, coating compositions for on seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils, as well as ULV cold mist and warm mist formulations.

These formulations may be produced in known manner, for example by mixing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.

As liquid solvents diluents or carriers, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or alkyl napthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethylsulphoxide, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.

As solid carriers there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers for granules there may be used crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks.

As emulsifying and/or foam-forming agents there may be used non-ionic and anionic emulsifiers, such as polyoxyethylene-acid esters, polyoxyethylene-alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysis products.

Dispersing agents include, for example, lignin sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulation.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as align dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese boron, copper, cobalt, molybdenum and zinc.

The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.

The active compounds according to the invention, as such or in the form of their formulations, can also be used, for combating weeds, as mixtures with known herbicides, finished formulations or tank mixes being possible.

Mixtures with other known active compounds, such as herbicides, fungicides, insecticides, acadcides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, are also possible.

The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules.

They are used in the customary manner, for example by watering, spraying, atomizing or scattering.

The active compounds according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing. They are used, in particular, after emergence of the plants.

The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 0.001 and 10 kg of active compound per hectare of soil surface, preferably between 0.01 and 5 kg per ha.

The preparation and use of the active compounds according to the invention can be seen from the following examples.

EXAMPLE 1 ##STR20##

1-(2-chloro-3-pyridyl)-5(4H)-tetrazolinone (1.0 g), diethylcarbamoyl chloride (0.7 g) and 4-dimethylaminopyridne (0.7 g) were suspended in toluene (15 ml). The resulting suspension was heated under reflux for 6 hours. The salts were removed, by filtration, and the solvent was distilled off under reduced pressure. The resulting residue was subjected to a silica gel chromatography (chloroform) so that 1-(2-chloro-3-pyridyl )-4-(N,N-diethylcarbamoyl)-5(4H)-tetrazolinone(1.3 g) was obtained.

n_(D) ²⁰ =1.5511

Further compounds obtainable by the above-mentioned reaction procedure are shown in Table 3-1.

                  TABLE 3-1                                                        ______________________________________                                          ##STR21##                                                                     Compound                                                                       No.     Q       R.sup.1   R.sup.2 Physical Constant                            ______________________________________                                         2       Q2      ethyl     ethyl   n.sub.D.sup.20 = 1.5426                      3       Q3      ethyl     ethyl   m.p. 72.5-75° C.                      4       Q5      methyl    isopropyl                                                                              m.p. 99.5-101° C.                     5       Q5      ethyl     isopropyl                                                                              m.p. 87.5-89.5° C.                    6       Q5      ethyl     cyclohexyl                                                                             m.p. 56.5-60° C.                      7       Q5      allyl     allyl   n.sub.D.sup.20 = 1.5616                      8       Q5      propargyl propargyl                                                                              m.p. 142-145.5° C.                    9       Q7      ethyl     ethyl   m.p. 61-62° C.                        10      Q11     methyl    isopropyl                                                                              n.sub.D.sup.20 = 1.5561                      11      Q11     ethyl     ethyl   m.p. 70-71.5° C.                      12      Q12     ethyl     ethyl   m.p. 63-67° C.                        13      Q12     ethyl     isopropyl                                                                              n.sub.D.sup.20 = 1.5579                      14      Q14     ethyl     ethyl   m.p. 51.5-53.5° C.                    15      Q14     ethyl     isopropyl                                                                              n.sub.D.sup.20 = 1.5388                      ______________________________________                                    

                  TABLE 3-2                                                        ______________________________________                                         Compound                                                                       No.     Q       R.sup.1  R.sup.2 Physical Constant                             ______________________________________                                         16      Q19     methyl   isopropyl                                                                              m.p. 115.5-118.5° C.                   17      Q19     ethyl    ethyl   m.p. 68.5-72.5° C.                     18      Q19     ethyl    isopropyl                                                                              n.sub.D.sup.20 = 1.5685                       19      Q24     ethyl    ethyl   n.sub.D.sup.20 = 1.5032                       20      Q26     methyl   isopropyl                                                                              m.p. 113.5-115.5° C.                   21      Q26     ethyl    ethyl   m.p. 104-109.5° C.                     22      Q26     ethyl    isopropyl                                                                              m.p. 105-109° C.                       23      Q27     ethyl    ethyl   m.p. 119.5-120.5° C.                   24      Q29     methyl   isopropyl                                                                              m.p. 112-115° C.                       25      Q29     ethyl    ethyl   m.p. 105.5-107.5° C.                   26      Q29     ethyl    isopropyl                                                                              m.p. 126-128° C.                       27      Q30     methyl   isopropyl                                                                              m.p. 124.5-127.5° C.                   28      Q30     ethyl    ethyl   n.sub.D.sup.20 = 1.5442                       29      Q30     ethyl    isopropyl                                                                              n.sub.D.sup.20 = 1.5397                       30      Q41     ethyl    ethyl   m.p. 87.5-90.5° C.                     ______________________________________                                    

Synthesis of starting materials

EXAMPLE 2 ##STR22##

2-Chloroisonicotinic acid (4.7 g) and thionyl chloride (10.0 g) were mixed and the resulting mixture was heated under reflux for 2 hours. The excess thionyl chloride was distilled off under reduced pressure, and trimethylsilyl azide (10.0 g) was added to the residue thus obtained. The resulting mixture was heated under reflux for 24 hours, and the excess trimethylsilyl azide was distilled off under reduced pressure and then methanol was added to the residue thus obtained. Thereafter, the methanol was distilled off and the resultant residue was subjected to a silica gel chromatography, using chloroform:ethanol=15: 1, so that 1-(2-chloro-4-pyridyl)-5(4H)-tetrazolinone (4.6 g) was obtained.

m.p. 182.5°-184° C. (decomposition).

1-(3-Pyridyl)-5(4H)-tetrazolinone (1.0 g) was obtained by the same process as was used in the Example 2 with the exception that nicotinic acid (1.1 g) was used instead of 2-chloroisonicotinic acid.

m.p. 201.5°-202.5° C.

1-(4-Pyridyl)-5(4H)-tetrazolinone (3.3 g) was obtained by the same process as was used in the Example 2 with the exception that isonicotinic acid (3.5 g) was used instead of 2-chloroisonicotinic acid.

m.p. more than 300° C.

1-(6-Chloro-3-pyridyl)-5(4H)-tetrazolinone (3.8 g) was obtained by the same process as was used in the Example 2 with the exception that 6-chloronicotinic acid (3.5 g) was used instead of 2-chloroisonicotinic acid.

m.p. 212°-212.5° C.

1-(3-Chloro-4-pyridyl)-5(4H)-tetrazolinone (1.8 g) was obtained by the same process as was used in the Example 2 with the exception that 3-chloroisonicotinic acid (4.7 g) was used instead of 2-chloroisonicotinic acid.

m.p. 176°-178.5° C. (decomposition).

1-(2-Methyl-3-pyridyl)-5(4H)-tetrazolinone (3.9 g) was obtained by the same process as was used in the Example 2 with the exception that, 2-methyl-nicotinic acid(4.1 g) was used instead of 2-chloroisonicotinic acid.

m.p. 174.5°-176° C. (decomposition).

1-(2-Methylthio-3-pyridyl)-5(4H)-tetrazolinone (4.5 g) was obtained by the same process as was used in the Example 2 with the exception that 2-methylthionicotinic acid (5.1 g) was used instead of 2-chlomisonicotinic acid.

m.p. 168° C. (decomposition).

1-(2-Chloro-6-methyl-3-pyridyl)-5(4H)-tetrazolinone (4.3 g) was obtained by the same process as was used in the Example 2 with the exception that 2-chloro-6-methylnicotinic acid (4.9 g) was used instead of 2-chloroisonicotinic acid.

m.p. 196°-197.5° C.

1-(4-trifluoromethyl-3-pyridyl)-5(4H)-tetrazolinone (1.2 g) was obtained by the same process as was used in the Example 2 with the exception that 4-trifluoromethylnicoticic acid (5.0 g) was used instead of 2-chloroisonicotinic acid.

m.p. 129.5°-132.5° C.

1-(2,6-Dichloro-4-pyridyl)-5(4H)-tetrazolinone (3.5 g) was obtained by the same process as was used in the Example 2 with the exception that 2,6-dichloroisonicotinic acid (6.8 g) was used instead of 2-chloroisonicotinic acid.

m.p. 123°-128° C.

EXAMPLE 3 ##STR23##

2-Chloro-3-pyridyl isocyanate (3.1 g) was mixed with trimethylsilyl azide (3.5 g), and the resulting mixture was heated under reflux for 20 hours. The excess trimethylsilyl azide was distilled off under reduced pressure, and methanol was added to the residue thus obtained. Thereafter, the methanol was distilled off, and the resultant residue was subjected to a silica gel column chromatography, using chloroform; ethanol=15:1, so that 1-(2-chloro-3-pyridyl)-5(4H)-tetrazolinone (3.0 g) was obtained.

m.p. 177.5°-178.5° C.

1-(2,6-Dichloro-4-pyridyl)-5(4H)-tetrazolinone (3.7 g) was obtained by the same process as was used in the Example 3 with the exception that 2,6-dichloro-4-pyridyl isocyanate (3.2 g) was used instead of 2-chloro-3-pyridyl isocyanate.

m.p. 191°-191.5° C.

1-(2,6-Dichloro-3-pyridyl)-5(4H)-tetrazolinone (3.5 g) was obtained by the same process as was used in the Example 3 with the exception that 2,6-dichloro-3-pyridyl isocyanate (5.7 g) was used instead of 2-chloro-3-pyridyl isocyanate.

m.p. 176°-177° C.

1-(2-Chloro-4-methyl-3-pyridyl)-5(4H)-tetrazolinone (4.1 g) was obtained by the same process as was used in the Example 3 with the exception that 2-chloro-4-methyl-3-pyridyl isocyanate (3.4 g) was used instead of 2-chloro-3-pyridyl isocyanate.

m.p. 160°-162° C.

EXAMPLE 4 ##STR24##

1-(2-Pyridyl)-5-methanesulfonyl-tetrazole (0.90 g) and tetrahydrofurane (15 ml) were added to water (1 ml) containing dissolved sodium hydroxide (0.80 g) and the resulting mixture was heated under reflux for 3. hours. After solvent was distilled off under reduced pressure, the resultant residue was subjected to a silica gel column chromatography, using chloroform:ethanol=15: 1, so that 1-(2-pyridyl)-5(4H)-tetrazolinone (0.2 g) was obtained.

m.p. 147°-147.5° C. (decomposition)

EXAMPLE 5

Starting material of Example 4 ##STR25##

1-(2-Pyridyl)-5-methylthiotetrazole(1.5 g), OXONE® (9.6 g ), water (15 ml) and ethanol (45 ml) were mixed and the resulting mixture was stirred at room temperature for 24 hours. After solvent was distilled off under reduced pressure, the resultant residue was subjected to a silica gel column chromatography (chloroform) so that 1-(2-pyridyl)-5-methanesulfonyl-tetrazole (1.0 g) was obtained.

m.p. 110.5°-112° C.

EXAMPLE 6

Starting material of Example 5 ##STR26##

4-(2-Pyridyl)-3-thiosemicarbazide (12.2 g), suspended to water (30 ml),and dimethylsufate (9.15 g) was added to the suspension. The resulting suspension was stirred for 3 hours. To this solution concentrated hydrochloric acid (30 ml) was added and the solution was cooled to 0° C. An aqueous solution (15 ml) of sodium nitrite (5.8 g) was added dropwise to the solution while maintaining the temperature and, after having stirred at 0° C. for 2 hours, the solution was neutralized by potassium carbonate and then extracted with chloroform. After drying with anhydrous sodium sulfate, the residue was subjected to a silica gel column chromatography (chloroform) so that 1-(2-pyridyl)-5-methylthiotetrazole (2.0 g) was obtained.

m.p. 106°-108° C.

EXAMPLE 7

Starting material of Example 6 ##STR27##

Methyl N-(2-pyridyl)dithiocarbamate (22.6 g), hydrazine monohydrate (12.3 g) and ethanol (300 ml) were mixed and the resulting mixture was heated under reflux for 3 hours. After distilling off the solvent under reduced pressure, water was added to the residue thus obtained, and a deposited material was obtained by filtration and dried by air, so that 4-(2-pyridyl)-3-thiosemicarbazide (18.9 g) was obtained.

m.p. 192.5°-193° C.

EXAMPLE 8 ##STR28##

Anhydrous aluminum chloride (8.6 g) was added to dimethylformamide (50 ml) under ice-cooling and the resulting mixture was stirred for 15 minutes. Sodium azide (3.8 g) was further added to that mixture and the mixture obtained was stirred for 15 minutes. After said stirring, phenyl N-(2-pyridyl)carbamate (6.3 g) was added to the mixture, and the resulting mixture was stirred at 80° C. for 10 hours. The reaction solution was added to the mixture of sodium nitrite (4 g), water (500 ml) and ice (250 g). After acidifying with 10% hydrochloric acid solution (until coloring the potassium iodide starch paper), the solution was extracted by ethyl acetate, and then the ethyl acetate phase obtained was dried with sodium sulfate. Thereafter solvent was distilled off under reduced pressure, the resultant residue was subjected to a silica gel column chromatography, so that 1-(2-pyridyl)-5(4H)-tetrazolinone was obtained (0.2 g).

m.p. 147°-147.5° C. (decomposition).

EXAMPLE 9

Starting material of the Example 8 ##STR29##

2-Aminopyridine (9.4 g) was dissolved in pyridine (150 ml) and phenylchloroformate (15.7 g) was added dropwise to the resulting solution under cooling at 0° C. After stirring at 0° C. for 2 hours, the solvent was distilled off under reduced pressure, and water was added to the residue thus obtained. Deposited crystals were separated by filtration and dried by air to obtain phenyl N-(2-pyridyl) carbamate (18.9 g).

m.p. 161°-162.5° C.

EXAMPLE 10 ##STR30##

3-Amino-2-chloro-4-methylpyridine (4.3 g) was added to a solution of trichloromethyl chloformate (6.0 g) in ethyl acetate (100 ml) at 0° to 5° C. with stirring and the mixture was refluxed under heating for 6 hours. After removal of the solvent under reduced pressure, 2-chloro-4-methyl-3-pyridylisocyanate (4.9 g) was obtained. A mixture of 2-chloro-4-methyl-3-pyridylisocyanate (4.9 g) and trimethylsilyl azide (11 g) was refluxed under heating for 30 hours. After removal of excess trimethylsilyl azide under reduced pressure, methanol was added to the resulting residue. Thereafter, the methanol was distilled off under reduced pressure. The resulting residue was purified by flash column chromatography (eluent chloroform:ethanol=15:1) to obtain the desired 1-(2-chloro-4-methyl-3-pyridyl)-5(4H)-tetrazolinone (3.0 g). n.p. 160°-162° C.

Biological tests

EXAMPLE 11

(Pre-emergence soil treatment test on upland weeds)

Formulation of Active Compounds

Carrier: 5 parts by weight of acetone

Emulsifier: 1 part by weight of benzyloxy polyglycol ether

To prepare suitable formulations, 1 part by weight of each of the active compounds was mixed with the above-stated amounts of the carrier and the emulsifier, and the resulting emulsifiable concentrate was then diluted with water to the desired concentrations.

Test Procedure

In a greenhouse, a number of test pots each having an area of 120 cm² were charged with soil taken from a cultivated field. Seeds of barnyard-grass and wild amaranth (Amaranthus blitum) were sown onto the soil surfaces in the respective test pots and each of the thus sown soil surfaces was covered with a soil layer.

Predetermined dosages of the active compounds of formulations prepared as mentioned above were uniformly sprayed onto the soil surface in the respective test pots.

Four weeks after the spraying of the active compound formulations, the herbicidal effects on the weeds were determined. The herbicidal effects were rated according to the following assessment:

Completely killed 100%

Condition equivalent to non-treated pots 0%

In the above-mentioned test, for example, compound Nos. 1, 3, 4, 5, 11, 12, 13, 15, 17, 18, 21, 22, 25 and 26 according to the present invention showed 100% herbicidal effect against barnyard-grass and wild amaranth at a dosage of 1.0 kg/ha.

EXAMPLE 12

(Post-emergence foliage treatment on upland weeds)

Test Procedure

In a greenhouse, a number of test pots each having an area of 120 cm² were charged with soil taken from a cultivated field. Seeds of barnyard-grass and wild amaranth (Amaranthus blitum) were sown onto the soil surfaces in the respective test pots and each of the thus sown soil surfaces was covered with a soil layer.

Ten days after sowing (average 2 leaf stage of weeds), predetermined dosages of active compounds of formulations prepared as in Example 10 were uniformly sprayed onto the foliage portions of the test plants in the respective test pots.

Three weeks after the spraying of the active compound formulations, the herbicidal effects on the weeds were determined.

In the above-mentioned test, for example, the compounds Nos. 1, 4, 13, 15 and 22 according to the present invention showed 100% herbicidal effect against barnyard-grass and wild amaranth at a dosage of 1.0 kg/ha.

It will be appreciated that the instant specification and the claims are set forth by way of illustration and not limitation, and that various modification and changes my be made without departing from the spirit and scope of the present invention. 

We claim:
 1. A pyridyltetrazolinone of the formula ##STR31## in which R¹ is C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₃₋₈ cycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₃₋₆ alkynyl or phenyl, andR² is C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₃₋₈ cycloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₃₋₆ alkynyl or phenyl, or R¹ and R² together with the nitrogen atom to which they are bonded are pyrrolidinyl, 2,5-dimethylpyrrolidinyl, pyrrolinyl, 2,5-dimethyl-3-pyrrolinyl, piperidyl, 2-methylpiperidyl, 2,6-dimethylpiperidyl, piperazinyl, morpholinyl, 1,2,3,4-tetrahydroquinolyl or 2-methyl-1,2,3,4-tetrahydroquinolyl, n is 0, 1, 2, or 3, and R³ is nitro, fluoro, chloro, bromo, C₁₋₄ haloalkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄ alkylthio or phenoxy.
 2. A compound according to claim 1, in whichR¹ is C₁₋₄ alkyl, C₁₋₄ haloalkyl, cyclopropyl, cyclopentyl, cyclohexyl, C₂₋₄ alkenyl, C₂₋₄ haloalkenyl, C₃₋₄ alkynyl phenyl, and R² is C₁₋₄ alkyl, C₁₋₄ haloalkyl, cyclopropyl, cyclopentyl, cyclohexyl, C₂₋₄ alkenyl, C₂₋₄ haloalkenyl, C₃₋₄ alkynyl or phenyl, n is 0, 1 or 2, and R³ each independently is nitro, fluoro, chloro, bromo, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄ alkylthio or phenoxy.
 3. A compound according to claim 1, wherein such compound is 1-(2-chloro-3-pyridyl)-4-(N,N-diethylcarbamoyl)-5(4H)-tetrazolinone of the formula ##STR32##
 4. A compound according to claim 1, wherein such compound is 1-(2-chloro-3-pyridyl)-4-(N-methyl-N-isopropyl)-5(4H)-tetrazolinone of the formula ##STR33##
 5. A compound according to claim 1, wherein such compound is 1-(3-chloro-4-pyridyl)-4(N-ethyl-N-isopropyl-carbamoyl)-5(4H)-tetrazolinone of the formula ##STR34##
 6. A compound according to claim 1, wherein such compound is 1-(2-methyl-3-pyridyl)-4-(N-ethyl-N-isopropyl)-5(4H)-tetrazolinone of the formula ##STR35##
 7. A compound according to claim 1, wherein such compound is 1-(2,6-dichloro-3-pyridyl)-4-(N-ethyl-N-isopropyl)-5(4H)-tetrazolinone of the formula ##STR36##
 8. A herbicidal composition comprising a herbicidally effective amount of a compound according to claim 1 and a diluent.
 9. A method of combating unwanted vegetation which comprises applying to such vegetation or to a locus from which it is desired to exclude such vegetation a herbicidally effective amount of a compound according to claim 1 and a diluent.
 10. The method according to claim 10, wherein such compound is1-(2-chloro-3-pyridyl)-4-(N,N-diethylcarbamoyl)-5(4H)-tetrazolinone, 1-(2-chloro-3-pyridyl)-4-(N-methyl-N-isopropyl)-5(4H)-tetrazolinone, 1-(3-chloro-4-pyridyl)-4-(N-ethyl-N-isopropyl-carbamoyl)-5-(4H)-tetrazolinone, 1-(2-methyl-3-pyridyl)-4-(N-methyl-N-isopropyl)-5(4H)-tetrazolinone, or 1-(2,6-dichloro-3-pyridyl)-4-(N-methyl-N-isopropyl)-5(4H)-tetrazolinone. 